EP2185616A1

EP2185616A1 - Reactive isocyanate compositions

Info

Publication number: EP2185616A1
Application number: EP08864667A
Authority: EP
Inventors: Emmanouil Spyrou
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2007-12-21
Filing date: 2008-12-08
Publication date: 2010-05-19
Also published as: US8674050B2; WO2009080479A1; DE102007062316A1; US20100249310A1; JP2011510105A; CN101463119A

Abstract

The invention relates to compositions having isocyanate groups, which are to be cured without components reactive relative to isocyanate, a method for producing such compositions and their use.

Description

Reactive isocyanate compositions

The invention relates to compositions containing isocyanate groups which are to be cured without an isocyanate-reactive component, to processes for producing such compositions and to their use.

Externally or internally blocked polyisocyanates are valuable crosslinkers for thermally crosslinkable polyurethane (PUR) paint and adhesive composition.

So describes z. For example, DE-OS 27 35 497 PUR coatings with excellent weathering and heat stability. The crosslinkers, the preparation of which is described in DE-OS 27 12 931, consist of ε-caprolactam blocked isocyanurate-containing isophorone diisocyanate. There are also known urethane, biuret or urea group-containing polyisocyanates whose isocyanate groups are also blocked.

The disadvantage of these externally blocked systems is the cleavage of the blocking agent during the thermal crosslinking reaction. Since the blocking agent can thus emit into the environment, special measures must be taken to clean the exhaust air and / or recovery of the blocking agent for environmental and occupational hygiene reasons. In addition, the crosslinkers have a low reactivity. Curing temperatures above 170 ° C are required.

DE-OS 30 30 539 and DE-OS 30 30 572 describe processes for the preparation of uretdione-containing polyaddition compounds whose terminal isocyanate groups are blocked irreversibly with monoalcohols or monoamines. Disadvantages are, in particular, the chain-breaking constituents of the crosslinkers, which lead to low network densities of the PUR varnish coatings and thus to moderate solvent resistance. Hydroxyl-terminated, polyaddition compounds containing uretdione groups are the subject of EP 669 353. Due to their functionality of two, they have improved resistance to solvents. The compositions based on these uretdione polyisocyanates have in common that they emit no volatile compounds in the curing reaction. However, the baking temperatures are at least 180 ° C at a high level.

In commercial 2K formulations, isocyanate-containing components are mixed with isocyanate-reactive components and reacted. This has the night part that must be paid to the appropriate stoichiometry, which in practice here again and again errors in the dosage or in the calculation comes. In addition, in highly reactive systems, the mixing must be optimal, which means an increased expenditure on equipment.

Moisture-curing polyurethane systems (eg DE 196 46 879) require no further reactant apart from the NCO component. However, these have the disadvantage that the curing takes a comparatively long time (1-4 weeks depending on the temperature and humidity) and depends significantly on environmental parameters.

The object of the present invention was therefore to find reactive isocyanate-containing compositions which are to be cured without the addition of reactants, but at least without the addition of stoichiometric amounts of reactants.

Surprisingly, it has been found that the compositions according to the invention fulfill the task.

The present invention relates to compositions containing reactive isocyanate groups, essentially containing A) at least one compound containing isocyanate groups, based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic compounds Diisocyanates and / or polyisocyanates whose NCO groups are optionally partially reacted with compounds having hydroxyl groups and / or amine groups, in a weight proportion, based on the total formulation, of 10 to 99.8%, B) at least one quaternary ammonium salt and / or phosphonium salt With

Halogens or organic or inorganic acid anions or hydroxide as counterion as catalyst, in a proportion by weight, based on the total formulation, of 0.1 to 3%,

C) at least one compound which carries epoxide groups, as a cocatalyst, in a proportion by weight, based on the total formulation, of 0.1 to 5%,

D) optionally at least one acid in monomeric or polymeric form in a proportion by weight, based on the total formulation, of 0.01 to 20%

E) optionally hydroxyl-containing compounds, in a weight fraction, based on the total formulation, of from 0.5 to 70%, F) optionally auxiliaries and additives, in a weight fraction, based on the total formulation, of from 0.001 to 50%,

G) optionally solvent, in a weight proportion, based on the total formulation, of 1 to 70%.

Another object of the invention is also a process for the preparation of the compositions of the invention.

The compositions of the invention are reactive. That is, the compositions cure at 80 to 160 ° C within 5 to 30 minutes.

As isocyanate-containing compounds, component A), a broad range of isocyanates based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic diisocyanates and / or polyisocyanates are in principle suitable. According to the invention diisocyanates such. Isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2,2'-

Dicyclohexylmethane diisocyanate / 2,4'-dicyclohexylmethane diisocyanate / 4,4'- Dicyclohexylmethane diisocyanate (H ₁₂ MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-tetramethylene diisocyanate / 2,4,4-t-methylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI) and tetramethylxylylene diisocyanate ( TMXDI) as compounds A) containing isocyanate groups. Very particular preference is given to using IPDI, 4,4'-H ₁₂ MDI and HDI. Of course, mixtures can also be used. These isocyanate-containing compounds are used either in pure form or in the form of their derivatives, for. Example, isocyanurates, allophanates, ureas, biurets and / or carbodiimides, in a weight fraction, based on the total formulation, from 10 to 99.8%, the pure or derivatized isocyanates can be reacted with hydroxyl groups or amine-bearing compounds, so that therefrom isocyanate groups having prepolymers as component A) result.

The implementation of these isocyanate group-carrying isocyanates

Isocyanate group-containing prepolymers component A) includes the reaction of the free NCO groups with hydroxyl-containing and / or amine-containing monomers or polymers, such as. As polyesters, polythioethers, polyethers, polycaprolactams, polyepoxides, polyester amides, polyamides, polyetheramines, polyurethanes or low molecular weight di-, th- and / or tetra alcohols as chain extenders and optionally monoamines and / or monoalcohols as chain terminators and has been frequently described (DE 198 51 182, DE 197 00 014, WO 98/34972, WO 97/466 093, EP 669 353, EP 669 354). For this purpose, not inventive catalysts such. B. DBTL used.

The excess content of monomeric isocyanates may optionally by distillation, for. B. with a Kurzweg- or thin film distillation from the prepolymer mixture A) are separated.

The NCO content of the prepolymer A) can vary between 1 and 45%, the Ratio of NCO / OH groups> 1.

Preference is given to polyesters having an OH number of 30 to 250 mg KOH / g and an average molecular weight of 250 to 6000 g / mol or monomeric dialcohols, such as. As ethylene glycol, propanediol (1, 2) and - (1, 3), 2,2-Dimethylpropandiol- (1, 3), butanediol (1, 4), hexanediol (1, 6), 2-methylpentanediol -1, 5, 2,2,4-trimethylhexanediol (1,6), 2,4,4-trimethylhexanediol (1,6), heptanediol (1,7), dodecanediol (1,12), octadecene -9,10-diol (1, 12), thiodiglycol, octadecanediol (1, 18), 2,4-dimethyl-2-propylheptanediol (1, 3), diethylene glycol, ethylene glycol, tetraethylene glycol, trans and cis-i ^ -cyclohexanedimethanol used.

As catalysts under B), quaternary ammonium salts and / or quaternary phosphonium salts with halogens or organic or inorganic acid anions are used as the counterion. Examples are tetramethylammonium, tetramethylammonium, Tetramethylammoniumpropionat, Tetramethylammoniumbutyrat, tetramethylammonium, tetramethylammonium, tetraethylammonium, tetraethylammonium, Tetraethylammoniumpropionat, Tetraethylammoniumbutyrat, tetraethylammonium, tetraethylammonium ,, Tetrapropylammoniumformiat, Tetrapropylammoniumacetat, Tetrapropylammoniumpropionat, Tetrapropylammoniumbutyrat, Tetrapropylammoniumbenzoat, tetrapropylammonium, tetrabutylammonium, tetrabutylammonium, Tetrabutylammoniumpropionat, Tetrabutylammoniumbutyrat, tetrabutylammonium benzoate, Tetrabutylammonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium formate, ethyltriphenylphosphonium acetate, tetrabutylphosphonium benzotriazolate, tetraphenylphosphonium phenolate, thhexyltetradecylphosphonium decanoate, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride, Benzyltrimethylammonium fluoride, tetrabutylphosphonium hydroxide, tetrabutylphosphonium fluoride, tetrabutylammonium chloride,

Tetrabutylammoniumbronnid, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, Tetramethylammoniunnbronnid, tetramethylammonium iodide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, Benzyltripropylammoniumchlond, benzyltributylammonium chloride, methyltributylammonium chloride, Methyltripropylammoniumchlorid, methyltriethylammonium, Methyltriphenylammoniumchlorid, phenyltrimethylammonium, Benzyltrimethylammoniunnbronnid, Benzyltriethylammoniunnbronnid, Benzyltripropylammoniumbronnid, Benzyltributylammoniumbronnid, Methyltributylammoniumbromid, Methyltripropylammoniumbronnid, Methyltriethylammoniunnbronnid, Methyltriphenylammoniumbronnid, Phenyltrimethylammonium bromide, benzyltrimethylammonium iodide, benzyltriethylammonium iodide, benzyltripropylammonium iodide, benzyltributylammonium iodide, methyltributylammonium iodide, methyltripropylammonium iodide, methyltriethylammonium iodide, methyltrip henylammonium iodide, phenyltrimethylammonium iodide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride and benzyltrimethylammonium fluoride. These catalysts may be added alone or in mixtures. They can also be encapsulated or polymer tethered. Preference is given to using tetraethylammonium benzoate and tetrabutylammonium hydroxide.

The proportion of catalysts B) can be from 0.1 to 3% by weight of the total formulation, preferably from 0.3 to 2% by weight of the total formulation.

As co-catalysts C) epoxides are used. In question come here z. B. Glycidyl ethers and glycidyl esters, aliphatic epoxides, diglycidyl ethers based on bisphenol A and glycidyl methacrylates. Examples of such epoxides are triglycidyl isocyanurate (TGIC, trade name Araldit 810, Huntsman), mixtures of terephthalic acid diglycidyl ester and trimellitic triglycidyl ester (trade name Araldit PT 910 and 912, Huntsman), glycidyl ester of versatic acid (trade name Kardura E10, Shell), 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (ECC), diglycidyl ether based on bisphenol A (trade name EPIKOTE 828, Shell) ethylhexyl glycidyl ether, butyl glycidyl ether, pentaerythritol tetraglycidyl ether, (trade name Polypox R 16, UPPC AG) as well as other polypoxy types with free epoxy groups. Preference is given to using Araldit PT 910 and / or 912.

The proportion of catalysts C) may be from 0.1 to 5 wt .-%, preferably from 0.3 to 2 wt .-% of the total formulation, and they may be contained alone or in mixtures.

Acids which are mentioned under D) are all substances, solid or liquid, organic or inorganic, monomeric or polymeric, which have the properties of a Bronsted or a Lewis acid. Examples include: sulfuric acid, acetic acid, benzoic acid, malonic acid, succinic acid, terephthalic acid, but also copolyesters or copolyamides having an acid number of at least 20. If present, the proportion of these acids in the total formulation between 0.01% and 20 wt .-% be, preferably between 0.1 and 5 wt .-%, and they may be contained alone or in mixtures.

As hydroxyl-containing compounds E) z. B. polymers with a

OH number of 20-500 mg KOH / gram, preferably 30 to 120 mg KOH / g used.

Polyesters, polyethers, polyacrylates, polyurethanes, polyethers and / or polycarbonates having an OH number of 20 to 500 (in mg KOH / gram) and an average molecular weight of 250 to 6000 g / mol are preferably used in the hydroxyl-containing polymers E) , Particularly preferred are hydroxyl-containing Polyester having an OH number of 20 to 150 and an average molecular weight of 500 to 6,000 g / mol. Of course, mixtures of such polymers can be used.

As polymer E) it is particularly preferred to use polyesters containing hydroxyl groups. The preferred carboxylic acids for the preparation of these polyesters may be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted by halogen atoms and / or unsaturated. Examples which may be mentioned are: succinic, adipic, cork, azelaic, sebacic, phthalic, terephthalic, isophthalic, trimellitic, pyromellitic, tetrahydrophthalic, hexahydrophthalic, hexahydroterephthalic, di- and tetrachlorophthalic , Endomethylentetrahydrophthal-, glutaric, maleic and fumaric acid or - as far as accessible - their anhydrides, terephthalic acid dimethyl ester, terephthalic acid bis-glycol ester, furthermore cyclic monocarboxylic acid, such as benzoic acid, p-tert-butylbenzoic acid or hexahydrobenzoic acid.

As polyhydric alcohols come z. As ethylene glycol, 1, 2- and 1, 3-propylene glycol, 1, 4- and 2,3-butylene glycol, di-ß-hydroxyethylbutandiol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, cyclohexanediol, bis- (1, 4-hydroxymethyl) -propane, 2-methylpropanediol-1, 3. 2-Methylpentanediol-1, 5, 2,2,4 (2,4,4) -trimethylhexanediol-1, 6, glycerol, trimethylolpropane, trimethylolethane, hexanetriol-1, 2,6, butanetriol-1, 2,4, tris - (.beta.-hydroxyethyl) isocyanurate, pentaerythritol, mannitol and sorbitol and diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polypropylene glycol, polybutylene glycol, xylylene glycol and hydroxypivalate neopentyl glycol ester for the preparation of the polyester E) in question.

Also mono- and polyesters from lactones, eg. B. ε-caprolactone or hydroxycarboxylic acids, eg. B. hydroxypivalic acid, ε-hydroxydecanoic acid, ε-hydroxycaproic acid, thioglycolic acid, can be used as starting materials for the preparation of the polymers E. Polyesters of the abovementioned polycarboxylic acids or derivatives thereof and polyphenols, such as hydroquinone, Bisphenol A, 4,4'-dihydroxybiphenyl or bis (4-hydroxyphenyl) sulfone; Polyester of carbonic acid, which consists of hydroquinone, diphenylolpropane, p-xylylene glycol, ethylene glycol, butanediol or hexanediol-1, 6 and other polyols by conventional condensation reactions, eg. B. with phosgene or diethyl or diphenyl carbonate, or from cyclic carbonates, such as glycol carbonate or vinylidene carbonate, are obtainable by polymerization in a known manner; Polyester of silicic acid, polyester of phosphoric acid, e.g. B. from methane, ethane, ß-chloroethane, benzene or styrene phosphoric acid, -phosphorsäurechlorid or -phosphorsäureester and polyalcohols or polyphenols of the type mentioned above; Polyester of boric acid; Polysiloxanes, such as. For example, the products obtained by hydrolysis of dialkyldichlorosilanes with water and subsequent treatment with polyalcohols, which are obtained by addition of polysiloxane dihydrides to olefins, such as allyl alcohol or acrylic acid, are suitable as starting materials for the preparation of the polymer E).

Preferred polyesters E) are z. B. also the reaction products of

Polycarboxylic acids and glycidic compounds, as z. B. in DE-OS 24 10 513 are described.

Examples of glycidyl compounds which can be used are esters of 2,3-epoxy-1-propanol with monobasic acids having 4 to 18 carbon atoms, such as glycidyl palmitate, glycidyl laurate and glycidyl stearate, alkylene oxides of 4 to 18 carbon atoms, such as butylene oxide, and Glycidyl ethers, such as octyl glycidyl ether.

The polyesters E) can be obtained in a conventional manner by condensation in an inert gas atmosphere at temperatures of 100 to 260 ° C, preferably 130 to 220 ° C, in the melt or in azeotropic procedure, as described for. In methods of organic chemistry (Houben-Weyl); Vol. 14/2, pages 1 to 5, 21 to 23, 40 to 44, Georg Thieme Verlag, Stuttgart, 1963, or CR Martens, Alkyd Resins, pages 51 to 59, Reinhold Plastics Appl. Series, Reinhold Publishing Comp., New York, 1961. As polymers E) are also hydroxy-functional polyethers and polycarbonates into consideration. Preferred polyethers may, for. Example by polyaddition of epoxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, 3,3-bis (chloromethyl) -oxabicyclobutane, tetrahydrofuran, styrene oxide or the bis (2.5) - epoxypropylether of diphenylolpropane, by cationic polymerization in the presence of Lewis acids, such as. B. boron trifluoride, or by anionic polymerization with alkali metal hydroxides or alkali metal or by addition of these epoxides, optionally in admixture or sequentially, to starting components with reactive hydrogen atoms, such as alcohols or amines, for. As water, ethylene glycol, polypropylene glycol (1, 3) or - (1, 2),

Pentamethylene glycol, hexanediol, decamethylene glycol, trimethylolpropane, glycerol, aniline, ammonia, ethanolamine, ethylenediamine, di- (ß-hydroxypropyl) -methylamine and hydroxyalkylated phenols, such as. For example, di- (β-hydroxyethoxy) -resorcinol.

Examples of mentioned polymers E) having carbonate groups can be known by reacting the exemplified dihydric or trihydric alcohols of the molecular weight range 62 to 300 with diaryl carbonates, such as. As diphenyl carbonate, phosgene or preferably cyclic carbonates, such as. B. trimethylene carbonate or 2,2-dimethyl-trimethylene carbonate (NPC) or mixtures of such cyclic carbonates. Particularly preferred carbonate diols are those which can be prepared from the dihydric alcohols mentioned as starter molecules and NPC with ring opening.

As polymers E) are also z. B. in polyurethane chemistry known polythioethers, polyacetals, polyepoxides, polyester amides or polyurethanes in the molecular weight range 250 to 8500 g / mol, which have isocyanate-reactive hydroxyl groups suitable.

Of course, it is also possible to use mixtures of the abovementioned polymers E) be used.

Suitable monomeric alcohols E) are mono-, di- or polyols of molecular weight of at least 32.

For example, the monoalcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols and hydroxymethylcyclohexane.

The diols are, for example, ethylene glycol, triethylene glycol, butanediol 1, 4, pentanediol 1, 5, hexanediol 1, 6, 3-methylpentanediol 1, 5, neopentyl glycol, 2,2,4 (2,4, 4) trimethylhexanediol and hydroxypivalic acid neopentyl glycol ester.

The triols are, for example, trimethylolpropane, dithmethylolpropane, trimethylolethane, hexanthol-1, 2,6, butantol-1, 2,4, tris (β-hydroxyethyl) -isocyanurate, pentaerythritol, mannitol or sorbitol.

For all hydroxyl-containing components E): The equivalence ratio of A) to E), ie the ratio of NCO / OH groups> 1, preferably NCO / OH> 1, 5, if E) present.

Auxiliaries and additives F) such as leveling agents, eg. As polysilicone or acrylates, light stabilizers z. As sterically hindered amines, or other auxiliaries, such as. As described in EP 669 353, be added in a total amount of 0.05 to 5 wt .-%. Fillers and pigments such. Titanium dioxide may be added in an amount of up to 50% by weight of the total composition.

Optionally, additional catalysts, such as those in polyurethane chemistry already are known to be included. These are mainly organometallic catalysts, such as. As dibutyltin dilaurate, or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2,] octane, in amounts of 0.001 -1 wt .-%.

Suitable solvents G) are all liquid organic and inorganic liquids which are inert under the reaction conditions. Examples which may be mentioned are acetone, ethyl acetate, butyl acetate, xylene, Solvesso 100, Solvesso 150, methoxypropyl acetate and dibasic ester.

The invention also provides a process for the preparation of the reactive

Isocyanate group-containing compositions by homogenization at upper temperature limits of 120 to 130 ° C.

The homogenization of all constituents for the preparation of the composition according to the invention can be carried out in suitable aggregates, such. As heated stirred tanks, kneaders, or extruders, carried out, with upper temperature limits of 120 to 130 ° C should not be exceeded. In the solid formulations, the application of ready to spray powders on suitable substrates by the known methods, such as. B. by electrostatic powder spraying, vortex sintering, or electrostatic vortex sintering. After application, the coated workpieces are heated to a temperature of 60 to 220 ° C for 4 to 60 minutes, preferably 6 to 30 minutes at 80 to 160 ⁰ C.

Another object of the present invention is the use of the compositions according to the invention containing reactive isocyanate groups as a coating agent, in particular as a primer, interlayer, topcoat, clearcoat, adhesive or sealing material and the coating agent itself.

The invention also relates to the use of the compositions according to the invention containing reactive isocyanate groups for the production of liquid and powder paint coatings on metal, plastic, glass, wood, textile, MDF (Middle Density Fiber Boards) or leather substrates or other heat-resistant substrates.

The invention also relates to the use of compositions of the invention containing reactive isocyanate groups as adhesive compositions for bonding metal, plastic, glass, wood, textile, MDF (Middle Density Fiber Boards) or leather substrates or other heat-resistant substrates.

The invention also relates to metal coating compositions, in particular for automobile bodies, motor and bicycle parts, building parts and household appliances, wood coating compositions, glass coating compositions, textile coating compositions, leather coating compositions and

Plastic coating compositions containing the compositions containing reactive isocyanate groups according to the invention.

The coating can either be used alone or be a layer of a multi-layer construction. It can be applied, for example, as a primer, as an intermediate layer or as a topcoat or clearcoat. The layers above or below the coating can either be thermally cured conventionally or else by radiation.

The subject matter of the invention will be explained in more detail below with reference to examples.

Examples:

I. Starting materials: Table 1 :

T _G : glass transition point;

II. Preparation of the NCO Prepolymer

The OH polyester DYNACOLL 7150 (191 g) was dissolved in 150 ml of a mixture of butyl acetate (BA) and xylene (1: 1) and admixed with 0.02 g of DBTL. This mixture was added dropwise at 80 ° C within 30 min in 31, 7g IPDI. The mixture was stirred for a further 1.5 hours at this temperature and then cooled. The NCO content was then 1.6%. IN THE. Inventive Composition 1 and Comparison 2 * and 4 * Table 2:

^* Comparative examples according to the invention; weight

IV. Results

All formulation ingredients are combined and stirred for 20 minutes by means of a magnetic stirrer.

The ready-to-use formulation is knife-coated onto steel sheets (bonder sheets 1303) in a layer thickness of 20-25 μm and cured in a circulating air oven at 150 ° C. (30 minutes).

Table 3.

^* not according to the invention comparative examples Errichsentiefung according to DIN 53156, ball impact according to ASTM D 2794-93

Claims

claims

1. Reactive compositions containing isocyanate groups substantially comprising A) at least one compound containing isocyanate groups, based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic diisocyanates and / or polyisocyanates whose NCO groups optionally partially reacted with compounds containing hydroxyl groups and / or amine groups are, in a weight proportion, based on the total formulation, from 10 to 99.8%,

B) at least one quaternary ammonium salt and / or quaternary phosphonium salt with halogens or organic or inorganic acid anions or hydroxide as counterion as catalyst, in a weight fraction, based on the total formulation, of 0.1 to 3%, C) at least one compound, the epoxy groups carries, as a cocatalyst, in a weight proportion, based on the total formulation, from 0.1 to 5%.

2. Reactive isocyanate-containing compositions according to claim 1, characterized in that it contains at least in addition one of the following components

D) at least one acid in monomeric or polymeric form in one

% By weight, based on the total formulation, of from 0.01 to 20% of E) hydroxyl-containing compounds, in a proportion by weight, based on the total formulation, of from 0.5 to 70%,

F) auxiliaries and additives, in a weight proportion, based on the total formulation, of 0.001 to 50%,

G) solvent, in a weight proportion, based on the total formulation, of 1 to 70%.

3. Reactive isocyanate group-containing composition according to at least one of the preceding claims, characterized in that as component A) compounds selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 2,2'-dicyclohexylmethane diisocyanate /

2,4'-dicyclohexylmethane diisocyanate / 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-

Trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI), toluidine diisocyanate (TDI) and / or

Tetramethylxylylene diisocyanate (TMXDI) are included.

4. Reactive compositions containing isocyanate groups according to claim 3, characterized in that as component A) IPDI, 4,4'H ₁₂ MDI and / or HDI are included.

5. Reactive isocyanate group-containing compositions according to at least one of the preceding claims, characterized in that the isocyanate group-containing compounds A) are reacted with hydroxyl and / or amine-containing monomers and / or polymers to isocyanate-containing prepolymers A), wherein the ratio of NCO / OH groups> 1 is.

6. Reactive isocyanate-containing compositions according to claim 5, characterized in that polymers selected from polyesters, polythioethers, polyethers, polycaprolactams, polyepoxides, polyesteramides, polyamides,

Polyetheramines, polyurethanes are used.

7. Reactive compositions containing isocyanate groups according to claim 6, characterized in that polyester having an OH number of 30 to 250 mg KOH / g and an average molecular weight of 250 to 6000 g / mol are used.

8. Reactive compositions containing isocyanate groups according to claim 5, characterized in that di-, tri- and / or tetra alcohols, monoamines and / or monoalcohols are used.

9. Reactive isocyanate group-containing compositions according to claim 8, characterized in that ethylene glycol, propanediol (1, 2) and - (1, 3), 2,2-dimethylpropanediol (1, 3), butanediol (1, 4) , Hexanediol (1,6), 2-methylpentanediol-1,5, 2,2,4-trimethylhexanediol (1,6), 2,4,4-trimethylhexanediol (1,6), heptanediol (1, 7), dodecane diol (1, 12), octadecene-9,10-diol (1, 12), thiodiglycol, octadecanediol (1, 18), 2,4-di-methyl-2-propylheptanediol (1, 3), diethylene glycol, triethylene glycol,

Tetraethylene glycol, trans and cis-1, 4-cyclo-hexanedimethanol, used alone or in mixtures.

10. Reactive isocyanate group-containing compositions according to at least one of the preceding claims, characterized in that isocyanurates, allophanates, ureas, biurets and / or carbodiimides in A) are included.

11. Reactive isocyanate group-containing compositions according to at least one of the preceding claims, characterized in that catalysts B) are selected from tetramethylammonium formate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetramethylammonium hydroxide, tetraethylammonium formate,

Tetraethylammonium acetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium benzoate, tetraethylammonium hydroxide, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate,

Tetrapropylammonium hydroxide, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate, tetrabutylammonium benzoate, tetrabutylammonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium formate, ethyltriphenylphosphonium acetate,

Tetrabutylphosphonium benzotriazolate, tetraphenylphosphonium phenolate, trihexyltetradecylphosphonium decanoate, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride, benzyltrimnethylammonium fluoride, tetrabutylphosphonium hydroxide, tetrabutylphosphonium fluoride,

Tetrabutylammonium chloride, tetrabutylammoniumbronnide, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, benzyltrimethylammonium chloride,

Benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride, methyltributylammonium chloride, methyltripropylammonium chloride, methyltriethylammonium chloride, methyltriphenylammonium chloride, phenyltrimethylammonium chloride, benzylthymethylammonium bromide, benzylethylammonium bromide,

Benzyltripropylammonium chloride, benzyltributylammoniumbronnide, Methyltributylammonium bromide, methyltripropylammoniumbronnicl, methyltriethylammoniumbromide, methyltriphenylammoniumbronnicl, phenyltrimethylammoniumbronnicl, benzyltrimethylammoniunnioclicl, benzyltriethylammoniunnioclicl, benzyltripropylammoniumiodide, benzyltributylammoniumiodide, methyltributylammoniumiodide,

Methyltripropylammonium iodide, methyltriethylammonium iodide, methyltriphenylammonium iodide, phenyltrimethylammonium iodide, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride and benzyltrimethylammonium fluoride. are included.

12. Reactive isocyanate group-containing compositions according to claim

1 1, characterized in that as component B) tetraethylammonium and / or

Tetrabutylammonium hydroxide are included.

13. Reactive isocyanate group-containing compositions according to at least one of the preceding claims, characterized in that as component C) glycidyl ethers and glycidyl esters, aliphatic epoxides, diglycidyl ethers based on bisphenol A and / or glycidyl methacrylates are included.

14. Reactive isocyanate-containing compositions according to claim

13, characterized in that triglycidyl isocyanurate, mixtures of Terephthalsäurediglycidylester and

Trimellitic triglycidyl ester, glycidyl ester of versatic acid, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycylohexanecarboxylate (ECC), diglycidyl ether based on bisphenol A, ethylhexyl glycidyl ether, butylglycidyl ether, Pentaerythritol tetraglycidyl ether, or other types of polypo with free epoxy groups, contained alone or in mixtures.

15. Reactive isocyanate-containing compositions according to at least one of the preceding claims, characterized in that as component D) sulfuric acid, acetic acid, benzoic acid, malonic acid, terephthalic acid, phthalic acid, copolyesters and / or copolyamides having an acid number of at least 20 are included.

16. Reactive compositions containing isocyanate groups according to at least one of the preceding claims, characterized in that as component E) polyesters, polyethers, polyacrylates, polyurethanes, polyethers and / or polycarbonates having an OH number of 20 to 500 mg

KOH / gram and an average molecular weight of 250 to 6000 g / mol are included.

17. Reactive isocyanate-containing compositions according to at least one of the preceding claims, characterized in that as component E) hydroxyl-containing polyesters having an OH number of 20 to 150 and an average molecular weight of 500 to 6000 g / mol are included.

18. Reactive isocyanate group-containing compositions according to at least one of the preceding claims, characterized in that as component E) reaction products of polycarboxylic acids and glycidic compounds are contained.

19. Reactive isocyanate group-containing compositions according to at least one of the preceding claims, characterized in that as component E) polythioethers, polyacetals, polyepoxides, polyester amides and / or polyurethanes of the molecular weight range 250 to

8500 g / mol, which contain isocyanate-reactive hydroxyl groups.

20. Reactive isocyanate group-containing compositions according to at least one of the preceding claims, characterized in that as component E) mono-, di- and / or polyols of molecular weight of at least 32 g / mol are included.

21. Reactive compositions containing isocyanate groups according to at least one of the preceding claims, characterized in that equivalence ratio of A) to E), ie the ratio of NCO / OH groups> 1, preferably NCO / OH> 1, 5.

22. A process for the preparation of compositions containing reactive isocyanate groups substantially containing

A) at least one compound containing isocyanate groups, based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic diisocyanates and / or polyisocyanates whose NCO groups are optionally partially reacted with compounds containing hydroxyl groups and / or amine groups, in a weight proportion, based on the Total formulation, from 10 to 99.8%,

B) at least one quaternary ammonium salt and / or quaternary phosphonium salt with halogens or organic or inorganic

Acid anions or hydroxide as a counterion as a catalyst, in one Weight fraction, based on the total formulation, of 0.1 to 3%,

C) at least one compound which carries epoxy groups, as a cocatalyst, in a weight fraction, based on the total formulation, of 0.1 to 5%, by homogenization at upper temperature limits of 120 to 130 ° C.

23. Use of reactive isocyanate groups

Compositions according to at least one of the preceding claims 1 to

21 from compositions containing reactive isocyanate groups in

Containing substantially

A) at least one isocyanate group-containing compound based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic

Diisocyanates and / or polyisocyanates whose NCO groups are optionally partially reacted with compounds containing hydroxyl groups and / or amine groups, in a weight proportion, based on the total formulation, of 10 to 99.8%, B) at least one quaternary ammonium salt and / or quaternary

Phosphonium salt with halogens or organic or inorganic acid anions or hydroxide as counterion as catalyst, in a proportion by weight, based on the total formulation, of 0.1 to 3%,

C) at least one compound which carries epoxy groups, as a cocatalyst, in a weight proportion, based on the total formulation, from 0.1 to

5%, as a coating agent.

24. Use according to claim 23 as a primer, intermediate layer, topcoat, clearcoat or sealing material.

25. Use according to claim 23 or 24 for the preparation of paint and adhesive compositions for metal, plastic, wood, textiles, glass, leather, MDF (Middle Density Fiber Boards) or other heat-resistant substrates.

26. A coating composition comprising reactive isocyanate groups having compositions according to at least one of the preceding claims 1 to 21 from

Phosphonium salt with halogens or organic or inorganic acid anions or hydroxide as a counterion as a catalyst, in a weight proportion, based on the total formulation, from 0.1 to 3%, C) at least one compound which carries epoxy groups, as a co-catalyst, in a weight proportion , based on the total formulation, from 0.1 to

5%.

27. A metal coating composition, comprising substantially isocyanate group-containing compositions of A) at least one isocyanate group-containing compound, based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic diisocyanates and / or polyisocyanates whose NCO groups optionally partially with hydroxyl groups and / or amine groups reacted compounds in a weight proportion, based on the total formulation, from 10 to 99.8%,

B) at least one quaternary ammonium salt and / or quaternary phosphonium salt with halogens or organic or inorganic acid anions or hydroxide as counterion as catalyst, in a weight fraction, based on the total formulation, of 0.1 to 3%, C) at least one compound, the epoxy groups carries as co-catalyst, in a weight proportion, based on the total formulation, from 0.1 to 5%.

28. A wood coating composition, comprising substantially isocyanate group-containing compositions of A) at least one isocyanate group-containing compound, based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic diisocyanates and / or polyisocyanates whose NCO groups optionally partially with hydroxyl groups and / or amine groups reacted compounds in a weight proportion, based on the total formulation, from 10 to 99.8%,

A leather coating composition or textile coating composition, substantially containing reactive

Isocyanate group-containing compositions

A) at least one compound containing isocyanate groups, based on aromatic, aliphatic, (cyclo) aliphatic or cycloaliphatic diisocyanates and / or polyisocyanates whose NCO groups are optionally partially reacted with compounds containing hydroxyl groups and / or amine groups, in a weight proportion, based on the Total formulation, from 10 to 99.8%.

B) at least one quaternary ammonium salt and / or phosphonium salt with halogens or organic or inorganic acid anions or hydroxide as counterion as catalyst, in a proportion by weight, based on the total formulation, of 0.1 to 3%, C) at least one compound which carries epoxide groups, as a cocatalyst, in a weight proportion, based on the total formulation, of 0.1 to 3%.

30. Plastic coating composition or

Glass coating compositions, essentially containing reactive isocyanate groups compositions

Acid anions or hydroxide as counterion as catalyst, in a proportion by weight, based on the total formulation, of 0.1 to 3%,

C) at least one compound which carries epoxy groups, as a cocatalyst, in a weight proportion, based on the total formulation, of 0.1 to 5%.

31. The metal coating composition of claim 27 for

Automotive bodies, motorcycles and bicycles, building parts and household appliances.

32. Coating compositions according to one of claims 27 to 31, characterized in that at least one of the components D) to G) is contained.

33. Coating compositions according to one of claims 27 to 32, characterized in that these compounds contain at least one of claims 2 to 21.